CN1209291C - Lithium-transition metal composite oxide - Google Patents

Lithium-transition metal composite oxide Download PDF

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CN1209291C
CN1209291C CNB018103529A CN01810352A CN1209291C CN 1209291 C CN1209291 C CN 1209291C CN B018103529 A CNB018103529 A CN B018103529A CN 01810352 A CN01810352 A CN 01810352A CN 1209291 C CN1209291 C CN 1209291C
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lithium
transition metal
composite oxide
particle
accumulative total
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CN1431972A (en
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数原学
汤川惠
齐藤尚
木村贵志
砂原一夫
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Sumitomo Chemical Co Ltd
AGC Seimi Chemical Ltd
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KIYOMI CHEMICAL CO Ltd
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    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
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    • C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
    • C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
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    • C01G53/00—Compounds of nickel
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    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract

A lithium-transition metal composite oxide which is represented by LixM1-yNyO2, wherein M is a transition metal element, N is a transition metal element other than M or an alkaline earth metal, 0.2 <= x <= 1.2, and 0 <= y <= 0.7, has gradients in a cumulative volume particle size distribution curve at cumulative volume percentages of 20 % and 80 % of 9 % / mu m or less and 3 % / mu m or more, respectively, and has an average particle diameter of 3 to 20 mu m. The lithium-transition metal composite oxide can be suitably used as a positive electrode active material of a lithium secondary cell which has a great volume capacity density, is high in safety, and is excellent in the homogeneous applicability of an electrolyte coating, in the durability of charge-discharge cycle and in low temperature characteristics.

Description

Lithium-transition metal composite oxide
Technical field
The present invention relates to laminate structure lithium-transition metal composite oxide, used the secondary lithium batteries of these composite oxides anodal and used this anodal battery.
Background technology
In recent years along with the lighting and wirelessization of machine, to small-sized, light weight and to have a requirement of nonaqueous electrolytic solution secondary battery of high-energy-density more and more higher.Nonaqueous electrolytic solution secondary battery is with the known LiCoO that comprises in the active substance 2, LiNiO 2, LiNi 0.8Co 0.2O 2, LiMn 2O 4, LiMnO 2Composite oxides Deng lithium and transition metal.
Wherein, positive active material uses lithium cobalt composite oxide (LiCoO 2), negative pole uses the lithium secondary battery of carbon dioxide process carbon electrodes such as lithium alloy, graphite, carbon fiber can obtain the high-voltage of 4V level, so be a kind of battery with high-energy-density that is widely used.
But positive active material has used LiCoO 2Non-aqueous secondary battery, in the unit volume capacity density and security that improve the anode electrode layer, exist the even screening characteristics problem of electrode coating, problem, the problem of weight capacity density or the problem that loading capacity significantly descends in low temperature that cycle characteristics that discharge capacity of the cell reduces gradually descends of carrying out along with charge and discharge cycles.
For the part in addressing these problems, the spy opens flat 6-243879 communique and has disclosed following technology, by making positive active material LiCoO 2The median size particle volume that reaches 3～9 μ m and particle diameter 3～15 μ m account for more than 75% of all volumes, approximate 19 ° of strength ratios with CuK α as 2 θ that measure in the radiogenic X-ray diffraction and reach particular value with 45 ° diffraction peak, thereby make active substance with good coating characteristic, self-discharge characteristics, cycle characteristics.This communique has further disclosed LiCoO 2The size distribution of particle is not below the 1 μ m or the more satisfactory state more than the 25 μ m.Yet,, can not obtain gratifying security, volume capacity density and weight capacity density though such positive active material has improved coating characteristic and cycle characteristics.
Also have, in order to improve anodal weight capacity density and charge, it is 0.1～50 μ m that the spy opens the median size that the 2000-82466 communique disclosed the lithium composite xoide particle, and has 2 positive active materials with the superiors in the size-grade distribution.There are 2 positive active materials in the size-grade distribution that has disclosed 2 kinds of different positive active materials mixing of median size simultaneously and made with the superiors.Above-mentioned technology can be improved anodal weight capacity density and charge sometimes, but be difficult to make anodal raw material powder, and can not get to satisfy simultaneously the material of anodal volume capacity density, security, even screening characteristics, weight capacity density, cycle characteristics requirement with 2 kinds of size distribution.
In addition, in order to solve the problem of battery behavior, open to have disclosed in the flat 3-201368 communique the spy and replace 5～35% technical scheme of Co atom with W, Mn, Ta, Ti or Nb so that to improve cycle characteristics be purpose.
In addition, the spy open disclosed in the flat 10-312805 communique use lattice parameter c axial length below 14.051 dusts, the crystallite diameter of (110) direction of crystallite is the hexagonal system LiCoO of 45～100nm 2As positive active material, thereby improved the technical scheme of cycle characteristics.
Also have, the spy opens to have disclosed in the flat 10-72219 communique and satisfies formula Li xNi 1-yN yO 2(in the formula, 0＜x＜1.1,0≤y≤1), primary particle be not tabular but column and (volume reference accumulative total 95% footpath one volume benchmark accumulative total, 5% footpath/volume reference accumulative total 5% directly) below 3, median size is the initial stage loading capacity height of the lithium composite xoide of 1～50 μ m, and the charge and discharge cycles weather resistance is good.
But, in above-mentioned conventional art, use lithium-transition metal composite oxide as also not finding the battery that can satisfy volume capacity density, security, even screening characteristics, cycle characteristics and cold property etc. simultaneously among the lithium secondary battery of positive active material.
The purpose of this invention is to provide have the comparatively large vol capacity density, higher, the even screening characteristics of security is good, the charge and discharge cycles weather resistance good and cold property is good as the lithium-transition metal composite oxide of the novelty of positive active material for lithium secondary battery, and the secondary lithium batteries positive pole and the lithium secondary battery that have used these composite oxides.
The announcement of invention
The invention provides lithium-transition metal composite oxide, contain general formula Li xM 1-yN yO 2(in the formula, 0.2≤x≤1.2,0≤y≤0.7, M is that transition metal, N are transition metal or the alkali earth metal beyond the M) the lithium composite xoide particle of expression, in the accumulative total volume particle size distribution curve of this lithium composite xoide, the accumulative total volume fraction be the gradient of 20% o'clock curve below 9%/μ m, the accumulative total volume fraction be the gradient of 80% o'clock curve more than 3%/μ m, and median size is 3～20 μ m.
As described below, the present inventor will possess that above-mentioned particular chemical is formed, size-grade distribution and when using as positive active material for lithium secondary battery based on the lithium-transition metal composite oxide of the specific collection of illustrative plates proterties of the crystalline texture in the X-ray diffraction, can obtain bigger volume capacity density, reliable security, good homogeneous screening characteristics, favorable charge-discharge cyclic durability and good cold property.
It is that what reason can obtain above-mentioned good characteristic that the present invention does not determine actually, but can consider in conjunction with forming as the particular chemical that contains transition metal of feature of the present invention, also can consider in accumulative total volume-size distribution curve, the accumulative total volume fraction is that the gradient of 20% o'clock curve is the gradient feature in specified range respectively of 80% o'clock curve with the accumulative total volume fraction, like this when making electrode with the lithium-transition metal composite oxide particle, the compression flow of the particle in the pressurization course of processing just becomes easy, thereby improved volume electrode weight, consequently can improve the electrode volume capacity.
Simple declaration to drawing
Fig. 1 represents the accumulative total volume distributed median curve of the lithium-transition metal composite oxide of the present invention in the example 1.
Fig. 2 represents the particle diameter curve of frequency distribution of the lithium-transition metal composite oxide of the present invention in the example 1.
Fig. 3 represents the accumulative total volume distributed median curve of the lithium-transition metal composite oxide in as a comparative example the example 8.
Fig. 4 represents the particle diameter curve of frequency distribution of the lithium-transition metal composite oxide in as a comparative example the example 8.
The best mode that carries out an invention
The present invention is described in more detail below to enumerate embodiment preferably of the present invention.
Lithium-transition metal composite oxide of the present invention formula Li xM 1-yN yO 2(in the formula, 0.2≤x≤1.2,0≤y≤0.7, M is that transition metal, N are transition metal or the alkali earth metal beyond the M) expression.M represents transition metal, comprises the metallic element of the 4th family, 5 families, 6 families, 7 families, 8 families, 9 families, 10 families and 11 families of the periodic table of elements.Wherein, Co, Ni or Mn are more satisfactory.In addition, N represents transition metal or the alkaline earth element except that M, and wherein, transition metal is as described in the M, and alkali earth metal comprises Ca, Mg, Sr, Ba etc.
In addition, as mentioned above, x satisfies 0.2≤x≤1.2, from the angle of capability retention, is preferably 0.98≤x≤1.02.Y satisfies 0≤y≤0.7, selects y from above-mentioned scope, and replaces part transition metal M in the above-mentioned general formula with N, can improve the performances such as high temperature preservation characteristics, cryogenic discharging characteristic, cycle characteristics, security of lithium secondary battery.
When the M in the following formula is Co or Ni, can improve charge and discharge cycles stability, weight capacity density and volume capacity density, so desirable especially.When M was Co, N preferably was selected from least a kind of element of Ti, Zr, Hf, V, Nb, Ta, Mg, Ca, Sr, Ba, Al, Fe, Mn.Wherein, from additive effect and capability retention, free from environmental pollution, cost equal angles, N is preferably Ti, Zr, Hf, V, Nb or Ta.In addition, consider that y preferably satisfies 0＜y≤0.05, consider that y preferably satisfies 0.0005≤y≤0.02 from additive effect and capability retention from capability retention.
When M is Ni, consider that from cycle characteristics N is preferably Co.Consider that from capability retention and additive effect y preferably satisfies 0.01≤y≤0.4.For example, LiNi 0.8Co 0.2O 2It is more satisfactory composition.And, replace a part with Al, Mn, Ti as the Co of element N, can improve security, capacity and discharge characteristic.Wherein, the most handy manganese or aluminium replace, and replace the 50%～20% the most desirable of cobalt element specifically.When having relatively high expectations security, LiNi 0.6Co 0.3Mn 0.1O 2, LiNi 0.7Co 0.2Al 0.1O 2, LiNi 0.6Co 0.2Mn 0.2O 2Desirable especially Deng composition.
The Ni-Mn stratiform composite oxides that contain lithium have the higher feature of security when being used for battery, so more satisfactory.It is that M is that Ni, N are Mn, 0.4≤y≤0.6 that ideal is formed, if y surpasses 0.6, then is difficult to keep hexagonal system, has consequently reduced the charge and discharge cycles weather resistance, so undesirable.
Also having M in addition is that Ni, N are that Co and Mn, 0.4≤y≤0.7, Co/Mn atomic ratio are 1/4～4/1 composition, if the Co/Mn atomic ratio surpasses 4/1, the effect of the raising security of manganese is reduced, and increases the usage quantity of high price cobalt simultaneously, so unsatisfactory.If less than 1/4 then reduces the first charge-discharge efficiency of battery, so also undesirable.
Also having M in addition is that Ni, N are that Co and Al or Mn, 0.1≤y≤0.4, Co/ (Al or Mn) atomic ratio are 1/4～4/1 composition, if y less than 0.1 then can reduce the security of battery, so undesirable.If y surpasses 0.4, then be reduced in the discharge characteristic in the big electric current, so also undesirable.
Lithium-transition metal composite oxide among the present invention have in accumulative total volume-size distribution curve the accumulative total volume fraction be the gradient (δ V/ δ R) of 20% o'clock curve below 9%/μ m and the accumulative total volume fraction be the feature of gradient (δ V/ δ R) more than 3%/μ m of 80% o'clock curve.In addition, the granularity in the above-mentioned accumulative total volume-size distribution curve among the present invention is meant the granularity of offspring, and the gradient of curve is meant the gradient of tangent line.
If the gradient that above-mentioned accumulative total volume fraction is 20% o'clock curve is more than 9%/μ m, then electrode density behind extrusion molding descends, and the result causes volume capacity density to descend, so undesirable.The accumulative total volume fraction be the gradient of 20% o'clock curve at 7.5%/μ m with next desirable especially.In addition, if the accumulative total volume fraction is gradient less than 3%/μ m of 80% o'clock curve, then electrode density behind extrusion molding descends, and the result causes volume capacity density to descend, so also undesirable.The accumulative total volume fraction is that the gradient of 80% o'clock curve is then desirable especially more than 4.5%/μ m.
Be not 2 peaks to occur in the curve of frequency distribution of lithium composite xoide particle of the present invention.Need mix active substance in order 2 peaks to occur, can raise the cost like this, so unsatisfactory with different-grain diameter distribution.Compare with the situation that 2 peaks occur, the present invention can obtain equating and even higher volume capacity.
Another feature of lithium transition-metal oxide of the present invention is that median size is 3～20 μ m.Median size is meant the volume average particle size of the offspring that the mutual aggegation of primary particle, sintering form.With the volume is that benchmark is obtained size-grade distribution, and as in 100% the accumulation curve, the particle diameter that accumulation curve reaches 50% point is expressed as volume reference accumulative total 50% footpath (D50) whole volumes.Frequency distribution and the accumulative total volume distributed median curve representation of size-grade distribution to measure with the laser light scattering particle size distribution device.
Of the present invention with whole volumes as in 100% the accumulation curve, the particle diameter that its accumulation curve reaches 5%, 20%, 80%, 95% point is called volume reference accumulative total 5% footpath (D5), volume reference accumulative total 20% footpath (D20), volume reference accumulative total 80% footpath (D80), volume reference accumulative total 95% footpath (D95).Particle diameter adopts in water medium and with ultrasonication etc. its abundant dispersive method to be measured (for example to use Leeds﹠amp; Northrup corporate system マ イ Network ロ ト ラ ッ Network HRAX-100 etc.).
Among the present invention, if the median size D50 deficiency of lithium-transition metal composite oxide 3 μ m, then because remove relatively difficulty of the following particle of particle diameter 1 μ m, thus lack security, voltage retentivity, the even screening characteristics of thick film, unsatisfactory.If D50 surpasses 20 μ m, then because remove relatively difficulty of the above particle of particle diameter 40 μ m, and, coarse grain produces uneven striped on the electrode applicator surface because of making, reduce the higher efficiency or the initial capacity of battery simultaneously easily, so also undesirable.It is desirable to median size D50 especially is 5～15 μ m.
More satisfactory in the lithium-transition metal composite oxide of the present invention is particle diameter less than the volume fraction of the particle of 1 μ m below 0.1%, and particle diameter surpasses the volume fraction of particle of 40 μ m below 0.5%.If particle diameter greater than 0.1%, then causes the decline of security or voltage retentivity, so undesirable less than the volume fraction of the particle of 1 μ m easily.If particle diameter surpasses the volume fraction of the particle of 40 μ m and surpasses 0.5%, then be easy to generate the inhomogeneous striped that causes by coarse grain, so also undesirable in the electrode applicator surface.Below 0.01%, and the volume fraction that particle diameter surpasses the particle of 40 μ m is being optimal below 0.1% to particle diameter less than the volume fraction of the particle of 1 μ m.
In addition, the volume reference of lithium-transition metal composite oxide of the present invention accumulative total 5% footpath D50 is more than 2 μ m, and volume reference accumulative total 95% footpath is more satisfactory below 30 μ m.Generally speaking, if D5 less than 2 μ m, then is difficult to remove the particle of particle diameter less than 1 μ m, security, voltage retentivity, the even screening characteristics of thick film are not ideal.If D95 surpasses 30 μ m; then be difficult to remove the particle that particle diameter surpasses 40 μ m generally speaking; and, cause that the higher efficiency of battery or first capacity descend simultaneously easily, so unsatisfactory because coarse grain can form uneven striped in the electrode applicator surface.Best is D5 is more than 3 μ m, and D95 is below 20 μ m.
Among the present invention especially ideal be the accumulative total volume fraction be 20% o'clock curve gradient below 7.5%/μ m, the accumulative total volume fraction be 80% o'clock curve gradient more than 4.5%/μ m and particle diameter less than the volume fraction of the particle of 1 μ m 0.01% below, particle diameter greater than the volume fraction of the particle of 40 μ m 0.1% below, simultaneously volume reference accumulative total 5% footpath more than the 3 μ m, volume reference adds up 95% lithium-transition metal composite oxide below 20 μ m directly.
The present invention also provides the lithium-transition metal composite oxide powder at 0.3t/cm 2Pressure down the particle diameter that obtains of pressurization compression back less than the volume fraction of the particle of 1 μ m at the lithium-transition metal composite oxide below 0.1%.The lithium-transition metal composite oxide powder is by adopting certain sintering method and sintering condition etc., can before making the coating slurry, make particle diameter reach 0.01 following % less than the volume fraction of the particle of 1 μ m, even but like this, on current collectoies such as aluminium foil, applying, in the process of dry pressurization, sometimes also the phenomenon that size distribution changes can appear then.This may be because when pressurization offspring the more weak part of cohesive force, cause distortion, the damage of offspring owing to the shearing force that adds man-hour.No matter be what reason, the decline that this phenomenon can cause battery security takes place, so undesirable.The method of the structural stability of the offspring of estimating these powder is studied the back find, use at 0.3t/cm 2Pressure down after the pressurization compression, particle diameter is very effective at the lithium-transition metal composite oxide below 0.1% less than the volume fraction of the particle of 1 μ m.Particle diameter 0.1% when above, can reduce the security of battery less than the volume fraction of the particle of 1 μ m.Best is at 0.3t/cm 2Pressure down after the pressurization compression, particle diameter less than the volume fraction of the particle of 1 μ m below 0.01%.
In addition, among the present invention the lithium-transition metal composite oxide powder at 0.3t/cm 2Pressure down pressurization processing back is from the aspect of the volume capacity density that improves electrode, the apparent density of powder is 2.9g/cm when M is Co or Ni 3, 3.1g/cm particularly 3Above is more satisfactory.Apparent density was 2.5g/cm when M was Ni in addition 3More than, 2.7g/cm particularly 3Above is more satisfactory.Apparent density is greater than 4, and the internal electrical resistive of battery is big when then using as electrode, so unsatisfactory.
Also have,, preferably use the less powder of offspring internal voids for anodal volume capacity density is filled, improved to the particle of lithium-transition metal composite oxide of the present invention by the pressurization compression with high-density.The voidage of offspring inside is measured with mercury porosimeter.Can obtain pore diameter generally speaking is the differential value and the integrated value (accumulative total pore volume cc/g) of the pore volume of 0.006～100 μ m.Specifically, the accumulative total pore volume of pore diameter below 1 μ m more satisfactory below 0.03cc/g is preferably below 0.01cc/g.
Also have, the M in the lithium-transition metal composite oxide of the present invention is that Co, y are 0 o'clock, is in the radiogenic X-ray diffraction device mensuration of carrying out with CuK α, the diffraction peak half-width of (110) face of 2 θ=66.5 ± 1 ° be 0.070～0.110 ° more satisfactory.The half-width of above-mentioned diffraction peak is represented the peak width at peak height 1/2 place, has reflected the crystallite diameter on the specific direction of the composite oxides that contain lithium, and relation is that the more little half-width of crystallite diameter is big more between the two.Above-mentioned half-width is during less than 0.070 °, reduces charge and discharge cycles weather resistance, initial capacity, average discharge voltage or security with its lithium secondary battery that uses as positive active material.If above-mentioned half-width surpasses 0.110 °, then can reduce the initial capacity and the security of lithium secondary battery.Above-mentioned peak width at half height is 0.080～0.100 ° of ideal especially.
In addition, M in the lithium-transition metal composite oxide of the present invention is Co, N is selected from Ti, Zr, Hf, V, Nb and Ta at least a kind, and y satisfies 0.0005≤y≤0.02 o'clock, with CuK α is in the radiogenic X-ray diffraction device mensuration of carrying out, the diffraction peak half-width of (110) face of 2 θ=66.5 ± 1 ° be 0.080～0.180 ° more satisfactory.If y is less than 0.0005, then the effect of cyclic durability and raising low-temperature working performance descends.If y greater than 0.02, then can make initial capacity descend, so also undesirable.More satisfactory is 0.001≤y≤0.01, is more preferably 0.002≤y≤0.007.If above-mentioned half-width less than 0.080 °, then can reduce its charge and discharge cycles weather resistance, initial capacity, average discharge voltage or security as the battery of positive electrode material use.If half-width surpasses 0.180 °, then can reduce the initial capacity and the security of battery, so also undesirable.Half-width is preferably 0.100～0.165 °.
In addition, when the M in the lithium-transition metal composite oxide of the present invention is Ni, used in the powder x-ray diffraction of CuK α line, near the diffraction peak half-width of (110) face 2 θ=65 ± 1 ° be 0.13～0.20 ° more satisfactory.Be preferably, N is Co, 0.1≤y≤0.4.If above-mentioned half-width less than 0.13 °, then can reduce charge and discharge cycles weather resistance, initial capacity, average discharge voltage or security.If above-mentioned half-width surpasses 0.20 °, initial capacity and security are descended, so also undesirable.Above-mentioned half-width is desirable especially in 0.14～0.17 ° scope.
Lithium-transition metal composite oxide of the present invention can in all sorts of ways and make, and there is no particular limitation to its manufacture method, but preferably uses following method.For example, when M was Co, the lithium source of this lithium cobalt composite oxide is Quilonum Retard or lithium hydroxide preferably.The cobalt source it is desirable to tricobalt tetroxide, alkali formula cobaltous hydroxide.Lithium cobalt composite oxide with size-grade distribution of the present invention and physics value can make with following method, promptly, the size-grade distribution and the specific surface area that need control cobalt source especially, and the mixed powder in lithium source and cobalt source under 700～1000 ℃ the temperature and the sintering processes of carrying out under the condition of oxygen 5～20 hours arranged, pulverizing and classification after the cooling of gained sinter, make lithium cobalt composite oxide with size-grade distribution of the present invention and physics value.When using tricobalt tetroxide, preferably using median size is that 1～20 μ m and specific surface area are 0.5～5m 2The powder of/g.When using alkali formula cobaltous hydroxide, preferably using median size is that 1～20 μ m and specific surface area are 2～200m 2The powder of/g.The median size of alkali formula cobaltous hydroxide particle is preferably 4～15 μ m.
When used lithium source was Quilonum Retard, preferably using median size was that 1～50 μ m and specific surface area are 0.1～10m 2The powder of/g.Lithium cobalt composite oxide of the present invention preferably makes by the alkali formula cobaltous hydroxide and the Quilonum Retard of mixed sintering as raw material.
When the M in the lithium-transition metal composite oxide of the present invention was Co, the raw material of element N can use oxide compound or oxyhydroxide.The object lesson of these oxide compounds or oxyhydroxide is, when N can use Ta during for tantalum 2O 5, N can use titanium oxide TiO during for titanium 2Titanium oxide comprises Detitanium-ore-type and rutile-type.Battery behavior is good when wherein using Detitanium-ore-type, so more satisfactory.When N can use Nb during for niobium 2O 5, can use ZrO during for zirconium 2When N can use HfO during for hafnium 2, N can use V during for vanadium 2O 5, V 2O 3, VO 2If the median size of these oxide compounds or oxyhydroxide surpasses 5 μ m, the skewness of element N in the positive active material particle inside then, thus the additive effect of the element N relevant with the battery performance aspect is descended, so undesirable.The median size preferably of these oxide compounds or oxyhydroxide is below 1 μ m, and good especially is below 0.3 μ m.
When the M in the lithium-transition metal composite oxide of the present invention is Co, if the not enough 1m of the specific surface area of the oxide compound of element N or oxyhydroxide 2/ g then can make reactivity worth descend, and the additive effect of consequently relevant with battery performance element N descends, so unsatisfactory.If the oxide compound of element N or the specific surface area of oxyhydroxide surpass 100m 2/ g, then because element N embeds in the lattice equably, thus can reduce the additive effect of the element N relevant with battery performance, so also undesirable.The oxide compound of element N or the specific surface area of oxyhydroxide are preferably 2～20m 2/ g.
M of the present invention is that the lithium nickel composite oxide of Ni also can in all sorts of ways and makes.As the lithium source Quilonum Retard or lithium hydroxide are arranged.The nickel source comprises nickel oxide, nickel oxyhydroxide, nickel hydroxide etc. preferably.Element M among the present invention is Ni, when element N is Co, uniform mixed hydroxides or uniform mixed oxide are made by methods such as co-precipitation in advance in nickel source and cobalt source, form the lithium-nickel-cobalt composite oxide of homogeneous then with Quilonum Retard or lithium hydroxide mixed sintering, thereby obtain heavy body and good cyclic durability, so be more satisfactory method.
Make secondary lithium batteries when anodal with lithium-transition metal composite oxide of the present invention, can make by in these composite oxide powers, mixing carbon series conductive material such as acetylene black, graphite, furnace treated black and tackiness agent.Above-mentioned tackiness agent can use poly(vinylidene fluoride), tetrafluoroethylene, polymeric amide, carboxymethyl cellulose and acrylic resin etc.
By using solvent or dispersion medium lithium-transition metal composite oxide powder, electro-conductive material and the tackiness agent of the invention described above are made slurry or mixing thing, then it is coated on the positive electrode collectors such as aluminium foil, stainless steel foil, makes the secondary lithium batteries positive plate.
Use lithium-transition metal composite oxide of the present invention can use porous polyethylene, porousness polypropylene film etc. as the dividing plate in the lithium secondary battery of positive active material.In addition, the solvent of the electrolyte solution of battery can use all kinds of SOLVENTS, wherein is preferably carbonic ether.Can use ring-type or linear carbonate.Cyclic carbonate comprises Texacar PC, ethylene carbonate (EC) etc.Linear carbonate can be used methylcarbonate, diethyl carbonate (DEC), carbonic acid ethyl methyl esters (EMC), carbonic acid methyl propyl ester, carbonic acid methyl isopropyl ester etc.
Above-mentioned carbonic ether can use separately also in the present invention can mix use more than 2 kinds.And can use with other solvent.In addition, according to negative electrode active material and with linear carbonate and cyclic carbonate, can improve discharge characteristic, cyclic durability and efficiency for charge-discharge sometimes.
In addition, in the lithium secondary battery of lithium-transition metal composite oxide of the present invention as the positive active material use, can use and contain that vinylidene fluoride-the R 1216 interpolymer (for example, ア ト ケ system corporate system, trade(brand)name カ イ Na one) or contain the gel polymer electrolyte of vinylidene fluoride-perfluoro propyl Vinyl Ether interpolymer.
The solute that adds in above-mentioned electrolyte solvent or the polymer dielectric can be that to be selected from negatively charged ion be ClO 4-, CF 3SO 3-, BF 4-, PF 6-, AsF 6-, SbF 6-, CF 3CO 2-, (CF 3SO 2) 2In the lithium salts of N-etc. more than a kind.The addition of solute in electrolyte solvent or polymer dielectric that above-mentioned lithium salts forms is 0.2～2.0mol/l.If concentration is not in aforementioned range, then ionic conductance descends, thereby causes electrolytical specific conductivity to descend.Concentration is preferably in the scope of 0.5～1.5mol/l.
In the lithium secondary battery of lithium-transition metal composite oxide of the present invention as the positive active material use, negative electrode active material can use and can adsorb the material that discharges lithium ion.There is no particular limitation to the material that forms this negative electrode active material, can use lithium metal, lithium alloy, carbon material, periodictable 14 and 15 family's metals to be the oxide compound of main body, carbon compound, carborundum compound, aktivton, titanium sulfide, norbide mixture etc.The carbon material can use the organic thermal cracking products under various thermo-cracking conditions maybe can use synthetic graphite, natural graphite, amorphous graphite, expanded graphite, flaky graphite etc.In addition, oxide compound can use with the compound of stannic oxide as main body.Negative electrode collector can use Copper Foil, nickel foil etc.With above-mentioned active substance and the mixing slurry of making of organic solvent, then this slurry is coated on the tinsel current collector, through super-dry and pressurization processing, can make negative pole.
There is no particular limitation to the shape of lithium cell that lithium-transition metal composite oxide of the present invention is used as positive active material, can select lamellar, film like, rugosity, cylindrical, cylindric, button-type with spirally wound bottom etc. according to different purposes.
Embodiment
Specify the present invention by the following examples, but the present invention is not limited among these embodiment.Example 1～example 7 and routine 14-17 are embodiments of the invention, and example 8～example 13 is comparative examples.
[example 1]
The ratio of mixture surface-area is 65m 2Alkali formula cobaltous hydroxide powder and the specific surface area of/g are 1.2m 2The Quilonum Retard powder of/g.Ratio of mixture becomes LiCoO after adopting sintering 2Ratio.After these 2 kinds of powder do are mixed, in air in 930 ℃ sintering temperature 12 hours.Make the median size of sinter reach about 10 μ m by pulverizing, classification, obtain LiCoO 2Powder.
Use X-ray diffraction device (the motor system RINT of society 2100 types of science) to through oversintering, pulverizing and fractionated LiCoO 2Powder is measured, and obtains its X ray diffracting spectrum.Use in the powder x-ray diffraction of CuK α line, near the diffraction peak half-width of (110) face 2 θ=66.5 ± 1 ° is 0.089 °.In addition, measured the accumulative total pore volume of pore diameter 0.006～1 μ m with mercury porosimeter, consequently, pore volume is below 0.01cc/g.
In addition, measured above-mentioned LiCoO with the laser light scattering particle size distribution device 2The size-grade distribution of powder, it the results are shown in table 1.Its accumulative total volume distributed median curve also is shown in table 1, and the particle diameter curve of frequency distribution is shown in table 2.According to these results as can be known, the particle diameter of D5 is 4.4 μ m, the particle diameter of D95 is 17.8 μ m, particle diameter is 0% less than the volume fraction of the particle of 1 μ m, particle diameter is 0% greater than the volume fraction of the particle of 40 μ m, the accumulative total volume fraction is that the gradient of 20% o'clock curve is 6.7%/μ m, and the accumulative total volume fraction is that the gradient of 80% o'clock curve is 6.4%/μ m, and median size D50 is 10.3 μ m.
With the hydraulic pressure stamping machine at 0.3t/cm 2Under the pressure to above-mentioned LiCoO 2After powder pressurizeed and processes, its apparent density was 3.15g/cm 3After particle after the pressurization processing scattered with hand, be placed on and use ultrasonic dispersing in the water, measure size distribution once more, consequently particle diameter is 0% less than the volume fraction of 1 μ m.
Above-mentioned LiCoO 2Powder and acetylene black and vinylidene fluoride powder add N-Methyl pyrrolidone and make slurry after mixing with 90/5/5 mass ratio, apply with the wing single face then and amplexiform on the aluminium foil of thick 20 μ m.Obtain not occurring on the applicator surface the level and smooth applicator surface of striped, and sticking paying property is also fine.Dry back obtains anode for lithium battery body plate by the roll-in calendering.The density that is recorded electrode layer by the weight per unit area of the thickness of the positive polar body in calendering back and electrode layer is 3.28g/cm 3
Then, to being used on the positive pole after the punching of above-mentioned positive polar body plate, the metallic lithium foil of thickness 500 μ m is used on the negative pole, negative electrode collector uses the nickel foil of thick 20 μ m, and dividing plate is the porousness polypropylene of used thickness 25 μ m then, the LiPF of electrolytic solution working concentration 1M 6(solute is LiPF to/EC+DEC (1: 1) solution 6EC and the mass ratio of the DEC mixing solutions that is 1: 1, the aftermentioned solvent is also as benchmark), in the argon gas glove box, assemble 3 simple and easy airtight boxlike lithium celies of stainless steel with above-mentioned materials.In addition, refill and join 1 and used the LiPF of concentration as 1M as electrolytic solution 6The simple and easy airtight cassette battery of stainless steel of/EC+DEC+EMC (1: 1: 2) solution.
To 1 used electrolytic solution is the battery of EC+DEC (1: 1) solution, in 25 ℃ with the standard charging of the load current of 1g positive active material 75mA to 4.3V, then, discharge into 2.5V, try to achieve the initial stage loading capacity in standard with the load current of 1g positive active material 75mA.Then, try to achieve volume capacity density by the density and the weight capacity of electrode layer.In addition, this battery is carried out continuously 30 times charge and discharge cycles test.Consequently, the initial stage volume capacity density of the anode electrode layer under 25 ℃, 2.5～4.3V is 441mAh/cm 3, having carried out 30 volume capacity density after the charge and discharge cycles test is 427mAh/cm 3, the capacity sustainment rate is 97%.
In addition, to used electrolytic solution is other 2 batteries of EC+DEC (1: 1) solution, one was charged 10 hours under 4.3V, another charged 12 hours under 4.7V, removed these 2 batteries then in the argon gas glove box, took out the positive polar body plate after charging, go out the circular hole that diameter is 3mm after washing this positive polar body plate, this positive polar body plate is sealed in the aluminum hull with EC, heats up, measure the heating starting temperature with the speed of differential scanning calorimetry with 5 ℃/minute.Consequently, the heating starting temperature that is charged to the battery of 4.3V is 162 ℃, and the heating starting temperature that is charged to the battery of 4.7V is 95 ℃.
In addition, be that the battery of EC+DEC+EMC (1: 1: 2) solution charges postcooling to-25 ℃ in 25 ℃ to used electrolytic solution.Then, standard with the load current of 1g positive active material 75mA discharges into 2.5V, by obtaining the initial stage loading capacity in-25 ℃, try to achieve 25 ℃ initial capacity is decided to be 100% o'clock capability retention in-25 ℃, consequently-25 ℃ the capability retention in is 88%.
[example 2]
Adopt the method same with example 1, the ratio of mixture surface-area is 87m 2Alkali formula cobaltous hydroxide powder and the specific surface area of/g are 1.0m 2The Quilonum Retard powder of/g.Ratio of mixture becomes LiCoO after adopting sintering 2Ratio.These 2 kinds of powder do to mix back and example 1 similarly in air in 900 ℃ sintering temperature 12 hours.
With mercury porosimeter measure through pulverizing, the accumulative total pore volume of pore diameter 0.006～1 μ m of powder that the classification median size reaches about 15 μ m, consequently, pore volume is below 0.01cc/g.
Same with example 1, measure these size-grade distribution through pulverizing and fractionated powder, consequently, the particle diameter of D5 is 7.4 μ m, and the particle diameter of D95 is 24.1 μ m, and particle diameter is 0% less than the volume fraction of the particle of 1 μ m, particle diameter is 0% greater than the volume fraction of the particle of 40 μ m, the accumulative total volume fraction is that the gradient of 20% o'clock curve is 5.8%/μ m, and the accumulative total volume fraction is that the gradient of 80% o'clock curve is 5.4%/μ m, and median size D50 is 15.3 μ m.
With the hydraulic pressure stamping machine at 0.3t/cm 2Pressure under to these powder pressurize processing after, its apparent density is 3.25g/cm 3After particle after the pressurization processing scattered with hand, put into the water ultrasonic dispersing again, the mensuration size distribution, consequently particle diameter is 0% less than the volume fraction of 1 μ m.
Adopt with the same method of example 1 and obtain X ray diffracting spectrum, used in the powder x-ray diffraction of CuK α line, near the diffraction peak half-width of (110) face 2 θ=66.5 ± 1 ° is 0.095 °.Adopt in addition with the same method of example 1 obtain the anode electrode layer initial stage volume capacity density, be charged to the heating starting temperature of the battery of 4.3V and 4.7V.Used concentration of electrolyte is the LiPF of 1M 6The initial stage volume capacity density of the anode electrode layer of the battery of/EC+DEC (1: 1) solution is 442mAh/cm 3, the heating starting temperature that is charged to 4.3V and is charged to the battery of 4.7V is respectively 161 ℃ and 92 ℃.In addition, to used electrolytic solution is that the battery of EC+DEC+EMC (1: 1: 2) solution charges postcooling to-25 ℃ in 25 ℃, standard with the load current of 1g positive active material 75mA discharges into 2.5V then, by obtaining the initial stage loading capacity in-25 ℃, try to achieve 25 ℃ initial capacity is decided to be 100% o'clock capability retention in-25 ℃, capability retention consequently ,-25 ℃ is 87%.
[example 3]
Adopt the method same with example 1, the ratio of mixture surface-area is 65m 2The alkali formula cobaltous hydroxide powder of/g, specific surface area are 1.2m 2The Quilonum Retard powder of/g and specific surface area are 9m 2The anatase titanium dioxide powder of/g.Ratio of mixture becomes LiCo after adopting sintering 0.998Ti 0.002O 2Ratio.These 3 kinds of powder do to mix back and example 1 similarly in air in 900 ℃ sintering temperature 12 hours.
Measure through pulverizing and the fractionated median size reaches the accumulative total pore volume of pore diameter 0.006～1 μ m of the powder of about 15 μ m with mercury porosimeter, consequently, pore volume is below 0.01cc/g.
Same with example 1, measure these size-grade distribution through pulverizing and fractionated powder, consequently, the particle diameter of D5 is 5.2 μ m, and the particle diameter of D95 is 25.9 μ m, and particle diameter is 0% less than the volume fraction of the particle of 1 μ m, particle diameter is 0% greater than the volume fraction of the particle of 40 μ m, the accumulative total volume fraction is that the gradient of 20% o'clock curve is 3.9%/μ m, and the accumulative total volume fraction is that the gradient of 80% o'clock curve is 4.9%/μ m, and median size D50 is 15.1 μ m.
With the hydraulic pressure stamping machine at 0.3t/cm 2Pressure under to these powder pressurize processing after, its apparent density is 3.30g/cm 3After particle after the pressurization processing scattered with hand, put into the water ultrasonic dispersing again, the mensuration size distribution, consequently, particle diameter is 0% less than the volume fraction of 1 μ m.
Adopt with the same method of example 1 and obtain X ray diffracting spectrum, used in the powder x-ray diffraction of CuK α line, near the diffraction peak half-width of (110) face 2 θ=66.5 ± 1 ° is 0.122 °.In addition, adopt with the same method of example 1 and obtain the LiPF that used concentration of electrolyte is 1M 6The initial stage volume capacity density of the anode electrode layer of the battery of/EC+DEC (1: 1) solution, the heating starting temperature that is charged to 4.3V and is charged to the battery of 4.7V.The initial stage volume capacity density of anode electrode layer is 444mAh/cm 3, the heating starting temperature that is charged to 4.3V and is charged to the battery of 4.7V is respectively 158 ℃ and 93 ℃.
In addition, to used concentration of electrolyte be the LiPF of 1M 6The battery of/EC+DEC+EMC (1: 1: 2) solution charges postcooling to-25 ℃ in 25 ℃, standard with the load current of 1g positive active material 75mA discharges into 2.5V then, by obtaining the initial stage loading capacity in-25 ℃, try to achieve 25 ℃ initial capacity is decided to be 100% o'clock capability retention in-25 ℃, capability retention consequently ,-25 ℃ is 94%.
[example 4]
Adopt the method same with example 1, the ratio of mixture surface-area is 87m 2The alkali formula cobaltous hydroxide powder of/g, specific surface area are 1.0m 2The Quilonum Retard powder of/g and specific surface area are 5.3m 2The niobium oxides Nb of/g 2O 5Powder.Ratio of mixture becomes LiCo after adopting sintering 0.998Nb 0.002O 2Ratio.These 3 kinds of powder do to mix the back in air in 900 ℃ sintering temperature 12 hours.
Measure through pulverizing, make after the classification median size to reach the accumulative total pore volume of pore diameter 0.006～1 μ m of the powder of about 10 μ m with mercury porosimeter, its as a result pore volume below 0.01cc/g.
Same with example 1, measure these size-grade distribution through pulverizing and fractionated powder, consequently, the particle diameter of D5 is 3.0 μ m, and the particle diameter of D95 is 17.7 μ m, and particle diameter is 0% less than the volume fraction of the particle of 1 μ m, particle diameter is 0% greater than the volume fraction of the particle of 40 μ m, the accumulative total volume fraction is that the gradient of 20% o'clock curve is 3.9%/μ m, and the accumulative total volume fraction is that the gradient of 80% o'clock curve is 6.0%/μ m, and median size D50 is 9.8 μ m.
With the hydraulic pressure stamping machine at 0.3t/cm 2Pressure under to these powder pressurize processing after, its apparent density is 3.32g/cm 3After particle after the pressurization processing scattered with hand, put into the water ultrasonic dispersing again, the mensuration size distribution, consequently, particle diameter is 0% less than the volume fraction of 1 μ m.
Adopt with the same method of example 1 and obtain X ray diffracting spectrum, used in the powder x-ray diffraction of CuK α line, near the diffraction peak half-width of (110) face 2 θ=66.5 ± 1 ° is 0.113 °.In addition, adopt with the same method of example 1 and obtain the initial stage volume capacity density of anode electrode layer, the heating starting temperature that is charged to 4.3V and is charged to the battery of 4.7V.Used concentration of electrolyte is the LiPF of 1M 6The initial stage volume capacity density of the anode electrode layer of the battery of/EC+DEC (1: 1) solution is 447mAh/cm 3, the heating starting temperature that is charged to 4.3V and is charged to the battery of 4.7V is respectively 157 ℃ and 93 ℃.In addition, to used concentration of electrolyte be the LiPF of 1M 6The battery of/EC+DEC+EMC (1: 1: 2) solution charges postcooling to-25 ℃ in 25 ℃.Then, standard with the load current of 1g positive active material 75mA discharges into 2.5V, and by obtaining the initial stage loading capacity in-25 ℃, the initial capacity of trying to achieve 25 ℃ is decided to be 100% o'clock capability retention in-25 ℃, capability retention consequently ,-25 ℃ is 94%.
In addition, the niobium oxides of above-mentioned example is substituted with tantalum oxide, zirconium white, obtain the lithium composite xoide powder, the positive pole that has used this powder is used for battery can confirms that equally battery characteristic at low temperatures improves effect.
[example 5]
Adopt the method same with example 1, the ratio of mixture surface-area is 65m 2The alkali formula cobaltous hydroxide powder of/g, specific surface area are 1.2m 2The Quilonum Retard powder of/g and specific surface area are 9m 2The anatase titanium dioxide powder of/g.Ratio of mixture becomes LiCo after adopting sintering 0.998Ti 0.002O 2Ratio.These 3 kinds of powder do to mix back and example 1 similarly in air in 850 ℃ sintering temperature 12 hours.
Measure through pulverizing and the fractionated median size reaches the accumulative total pore volume of pore diameter 0.006～1 μ m of the powder of about 15 μ m with mercury porosimeter, consequently, pore volume is below 0.01cc/g.
Same with example 1, measure these size-grade distribution through oversintering, pulverizing and fractionated powder, consequently, the particle diameter of D5 is 3.0 μ m, and the particle diameter of D95 is 17.7 μ m, and particle diameter is 0% less than the volume fraction of the particle of 1 μ m, particle diameter is 0% greater than the volume fraction of the particle of 40 μ m, the accumulative total volume fraction is that the gradient of 20% o'clock curve is 3.8%/μ m, and the accumulative total volume fraction is that the gradient of 80% o'clock curve is 5.7%/μ m, and median size D50 is 14.8 μ m.
With the hydraulic pressure stamping machine at 0.3t/cm 2Pressure under to these powder pressurize processing after, its apparent density is 3.22g/cm 3After particle after the pressurization processing scattered with hand, put into the water ultrasonic dispersing again, measure size distribution, particle diameter is 2.3% less than the volume fraction of 1 μ m, showing after pressurization is processed to have produced the micro mist of particle diameter less than 1 μ m.
Adopt with the same method of example 1 and obtained X ray diffracting spectrum, used in the powder x-ray diffraction of CuK α line, near the diffraction peak half-width of (110) face 2 θ=66.5 ± 1 ° is 0.121 °.In addition, adopt with the same method of example 1 and obtain the initial stage volume capacity density of anode electrode layer, the heating starting temperature that is charged to 4.3V and is charged to the battery of 4.7V.Used concentration of electrolyte is the LiPF of 1M 6The initial stage volume capacity density of the anode electrode layer of the battery of/EC+DEC (1: 1) solution is 443mAh/cm 3, the heating starting temperature that is charged to 4.3V and is charged to the battery of 4.7V is respectively 154 ℃ and 89 ℃.In addition, to used concentration of electrolyte be the LiPF of 1M 6The battery of/EC+DEC+EMC (1: 1: 2) solution charges postcooling to-25 ℃ in 25 ℃, standard with the load current of 1g positive active material 75mA discharges into 2.5V then, by obtaining the initial stage loading capacity in-25 ℃, try to achieve 25 ℃ initial capacity is decided to be 100% o'clock capability retention in-25 ℃, capability retention consequently ,-25 ℃ is 94%.
[example 6]
Except being 0.61m with specific surface area 2The tricobalt tetroxide of/g replaces outside the alkali formula cobaltous hydroxide, and other operations are same with example 1, make LiCoO 2Powder.Then, obtain the X ray diffracting spectrum of the powder behind the sintering equally with example 1.Used in the powder x-ray diffraction of CuK α line, near the diffraction peak half-width of (110) face 2 θ=66.5 ± 1 ° is 0.130 °.
Measure through pulverizing and the fractionated median size reaches the accumulative total pore volume of pore diameter 0.006～1 μ m of the powder of about 3 μ m with mercury porosimeter, consequently, pore volume is below 0.01cc/g.
The particle diameter of D5 is 0.45 μ m, the particle diameter of D95 is 4.6 μ m, particle diameter is 14% less than the volume fraction of the particle of 1 μ m, particle diameter is 0% greater than the volume fraction of the particle of 40 μ m, the accumulative total volume fraction is that the gradient of 20% o'clock curve is 4.1%/μ m, the accumulative total volume fraction is that the gradient of 80% o'clock curve is 5.5%/μ m, and median size D50 is 3.1 μ m.With the hydraulic pressure stamping machine at 0.3t/cm 2Pressure under to these powder pressurize processing after, its apparent density is 3.25g/cm 3
In addition, adopt with the same method of example 1 and obtain the initial stage volume capacity density of anode electrode layer, the heating starting temperature that is charged to 4.3V and is charged to the battery of 4.7V.Used concentration of electrolyte is the LiPF of 1M 6The initial stage volume capacity density of the anode electrode layer of the battery of/EC+DEC (1: 1) solution is 432mAh/cm 3, the heating starting temperature that is charged to 4.3V and is charged to the battery of 4.7V is respectively 145 ℃ and 83 ℃.In addition, to used concentration of electrolyte be the LiPF of 1M 6The battery of/EC+DEC+EMC (1: 1: 2) solution charges postcooling to-25 ℃ in 25 ℃, standard with the load current of 1g positive active material 75mA discharges into 2.5V then, by obtaining the initial stage loading capacity in-25 ℃, try to achieve 25 ℃ initial capacity is decided to be 100% o'clock capability retention in-25 ℃, capability retention consequently ,-25 ℃ is 89%.
[example 7]
Make the co-precipitation in carbon dioxide of nickel and cobalt ammine compound, coprecipitate is heated, obtain nickel-cobalt co-precipitation oxyhydroxide (atomic ratio 0.8: 0.2), mix this co-precipitation oxyhydroxide and lithium hydroxide monohydrate powder, 515 ℃ of following sintering 20 hours.Then, under accounting for the condition of oxygen-stream of nitrogen gas of 40 volume % and 770 ℃, oxygen carries out 8 hours sintering.Make median size reach about 9 μ m by pulverizing and classification behind the sintering.
Adopt the X ray diffracting spectrum that obtains the powder behind the sintering with the same method of example 1, used in the powder x-ray diffraction of CuK α line, near the diffraction peak half-width of (110) face 2 θ=65 ± 1 ° is 0.152 °.In addition, with the accumulative total pore volume of mercury porosimeter mensuration pore diameter 0.006～1 μ m, consequently, pore volume is below 0.01cc/g.
Measure these through pulverizing and the size-grade distribution of fractionated powder with the same method of example 1, consequently, the particle diameter of D5 is 3.3 μ m, the particle diameter of D95 is 18.6 μ m, particle diameter is 0% less than the volume fraction of the particle of 1 μ m, and particle diameter is 0% greater than the volume fraction of the particle of 40 μ m, and the accumulative total volume fraction is that the gradient of 20% o'clock curve is 5.1%/μ m, the accumulative total volume fraction is that the gradient of 80% o'clock curve is 6.4%/μ m, and median size D50 is 9.6 μ m.
With the hydraulic pressure stamping machine at 0.3t/cm 2Pressure under to after these powder pressurization processing, its apparent density is 3.21g/cm 3After particle after the pressurization processing scattered with hand, put into the water ultrasonic dispersing again, the mensuration size distribution, consequently, particle diameter is 0% less than the volume fraction of 1 μ m.
Adopt with the same method of example 1 and obtain X ray diffracting spectrum, used in the powder x-ray diffraction of CuK α line, near the diffraction peak half-width of (110) face 2 θ=66.5 ± 1 ° is 0.113 °.Adopt the method same, obtain and used above synthetic LiNi with example 1 0.80Co 0.20O 2The initial stage volume capacity density of the anode electrode layer of powder in 2.7～4.3V.Used concentration of electrolyte is the LiPF of 1M 6The initial stage volume capacity density of the anode electrode layer of the battery of/EC+DEC (1: 1) solution is 536mAh/cm 3
[example 8]
Except being 0.89m with specific surface area 2The tricobalt tetroxide of/g replaces outside the alkali formula cobaltous hydroxide, and other operations are same with example 1, make LiCoO 2Powder.Measure through pulverizing and the fractionated median size reaches the accumulative total pore volume of pore diameter 0.006～1 μ m of the powder of about 9 μ m with mercury porosimeter, consequently, pore volume is below 0.01cc/g.
Adopt with the same method of example 1 and measure size-grade distribution, its result shows in table 2.Figure 3 shows that accumulative total volume distributed median curve, Figure 4 shows that the particle diameter curve of frequency distribution.By these curves as can be known the particle diameter of D5 be 5.19 μ m, the particle diameter of D95 is 15.2 μ m, particle diameter is 0% less than the volume fraction of the particle of 1 μ m, particle diameter is 0% greater than the volume fraction of the particle of 40 μ m, the accumulative total volume fraction is that the gradient of 20% o'clock curve is 13.1%/μ m, the accumulative total volume fraction is that the gradient of 80% o'clock curve is 7.5%/μ m, and median size D50 is 8.9 μ m.With the hydraulic pressure stamping machine at 0.3t/cm 2Pressure under to these powder pressurize processing after, its apparent density is 2.85g/cm 3After particle after the pressurization processing scattered with hand, put into the water ultrasonic dispersing again, the mensuration size distribution, consequently, particle diameter is 0% less than the volume fraction of 1 μ m.
Adopt with the same method of example 1 and obtain X ray diffracting spectrum, used in the powder x-ray diffraction of CuK α line, near the diffraction peak half-width of (110) face 2 θ=66.5 ± 1 ° is 0.133 °.In addition, adopt with the same method of example 1 and obtain the initial stage volume capacity density of anode electrode layer, the heating starting temperature that is charged to 4.3V and is charged to the battery of 4.7V.Used concentration of electrolyte is the LiPF of 1M 6The initial stage volume capacity density of the anode electrode layer of the battery of/EC+DEC (1: 1) solution is 411mAh/cm 3, the heating starting temperature that is charged to 4.3V and is charged to the battery of 4.7V is respectively 151 ℃ and 88 ℃.In addition.To used concentration of electrolyte is the LiPF of 1M 6The battery of/EC+DEC+EMC (1: 1: 2) solution charges postcooling to-25 ℃ in 25 ℃, standard with the load current of 1g positive active material 75mA discharges into 2.5V then, by obtaining the initial stage loading capacity in-25 ℃, try to achieve 25 ℃ initial capacity is decided to be 100% o'clock capability retention in-25 ℃, capability retention consequently ,-25 ℃ is 89%.
[example 9]
Identical with example 1, the ratio of mixture surface-area is 30m 2Alkali formula cobaltous hydroxide powder and the specific surface area of/g are 0.35m 2The Quilonum Retard powder of/g.Ratio of mixture becomes LiCoO after adopting sintering 2Ratio.These 2 kinds of powder do to mix the back in air in 930 ℃ sintering temperature 12 hours, make LiCoO 2Powder.
Measure through pulverizing and the fractionated median size reaches the accumulative total pore volume of pore diameter 0.006～1 μ m of the powder of about 12 μ m with mercury porosimeter, consequently, pore volume is below 0.01cc/g.
Adopt the method same, measure through pulverizing and fractionated LiCoO with example 1 2The size-grade distribution of powder, consequently, the particle diameter of D5 is 6.3 μ m, the particle diameter of D95 is 19.3 μ m, particle diameter is 0% less than the volume fraction of the particle of 1 μ m, and particle diameter is 0% greater than the volume fraction of the particle of 40 μ m, and the accumulative total volume fraction is that the gradient of 20% o'clock curve is 10.3%/μ m, the accumulative total volume fraction is that the gradient of 80% o'clock curve is 7.1%/μ m, and median size D50 is 11.9 μ m.
With the hydraulic pressure stamping machine at 0.3t/cm 2Pressure under to these powder pressurize processing after, its apparent density is 2.91g/cm 3After particle after the pressurization processing scattered with hand, put into the water ultrasonic dispersing again, the mensuration size distribution, consequently, particle diameter is 0% less than the volume fraction of 1 μ m.
Adopt with the same method of example 1 and obtain X ray diffracting spectrum, used in the powder x-ray diffraction of CuK α line, near the diffraction peak half-width of (110) face 2 θ=66.5 ± 1 ° is 0.087 °.In addition, adopt with the same method of example 1 and obtain the initial stage volume capacity density of anode electrode layer, the heating starting temperature that is charged to 4.3V and is charged to the battery of 4.7V.Used concentration of electrolyte is the LiPF of 1M 6The initial stage volume capacity density of the anode electrode layer of the battery of/EC+DEC (1: 1) solution is 414mAh/cm 3, the heating starting temperature that is charged to 4.3V and is charged to the battery of 4.7V is respectively 157 ℃ and 88 ℃.In addition, to used concentration of electrolyte be the LiPF of 1M 6The battery of/EC+DEC+EMC (1: 1: 2) solution charges postcooling to-25 ℃ in 25 ℃, standard with the load current of 1g positive active material 75mA discharges into 2.5V then, by obtaining the initial stage loading capacity in-25 ℃, try to achieve 25 ℃ initial capacity is decided to be 100% o'clock capability retention in-25 ℃, capability retention consequently ,-25 ℃ is 88%.
[example 10]
Except being 1.2m with specific surface area 2The tricobalt tetroxide of/g replaces beyond the alkali formula cobaltous hydroxide, and other are operated with identical with example 1, make LiCoO 2Powder.Adopt the X ray diffracting spectrum that obtains the powder behind the sintering with the same method of example 1, used in the powder x-ray diffraction of CuK α line, near the diffraction peak half-width of (110) face 2 θ=66.5 ± 1 ° is 0.130 °.
Measure through pulverizing and the fractionated median size reaches the accumulative total pore volume of pore diameter 0.006～1 μ m of the powder of about 9 μ m with mercury porosimeter, consequently, pore volume is below 0.01cc/g.
The particle diameter of D5 is 5.22 μ m, the particle diameter of D95 is 15.9 μ m, particle diameter is 0% less than the volume fraction of the particle of 1 μ m, particle diameter is 0% greater than the volume fraction of the particle of 40 μ m, the accumulative total volume fraction is that the gradient of 20% o'clock curve is 20.3%/μ m, the accumulative total volume fraction is that the gradient of 80% o'clock curve is 14.7%/μ m, and median size D50 is 9.2 μ m.
With the hydraulic pressure stamping machine at 0.3t/cm 2Pressure under to these powder pressurize processing after, its apparent density is 2.72g/cm 3After particle after the pressurization processing scattered with hand, put into the water ultrasonic dispersing again, the mensuration size distribution, consequently, particle diameter is 0% less than the volume fraction of 1 μ m.
Adopt with the same method of example 1 and obtain the initial stage volume capacity density of anode electrode layer, the heating starting temperature that is charged to 4.3V and is charged to the battery of 4.7V.Used concentration of electrolyte is the LiPF of 1M 6The initial stage volume capacity density of the anode electrode layer of the battery of/EC+DEC (1: 1) solution is 399mAh/cm 3, the heating starting temperature that is charged to 4.3V and is charged to the battery of 4.7V is respectively 150 ℃ and 87 ℃.In addition, to used concentration of electrolyte be the LiPF of 1M 6The battery of/EC+DEC+EMC (1: 1: 2) solution charges postcooling to-25 ℃ in 25 ℃, standard with the load current of 1g positive active material 75mA discharges into 2.5V then, by obtaining the initial stage loading capacity in-25 ℃, try to achieve 25 ℃ initial capacity is decided to be 100% o'clock capability retention in-25 ℃, capability retention consequently ,-25 ℃ is 87%.
[example 11]
Except being 1.5m with specific surface area 2The tricobalt tetroxide of/g replaces outside the alkali formula cobaltous hydroxide, and other operations are identical with example 1, make LiCoO 2Powder.Adopt the X ray diffracting spectrum that obtains the powder behind the sintering with the same method of example 1, used in the powder x-ray diffraction of CuK α line, near the diffraction peak half-width of (110) face 2 θ=66.5 ± 1 ° is 0.135 °.
Measure through pulverizing and the fractionated median size reaches the accumulative total pore volume of pore diameter 0.006～1 μ m of the powder of about 10 μ m with mercury porosimeter, consequently, pore volume is below 0.01cc/g.
The particle diameter of D5 is 5.16 μ m, the particle diameter of D95 is 14.8 μ m, particle diameter is 0% less than the volume fraction of the particle of 1 μ m, particle diameter is 0% greater than the volume fraction of the particle of 40 μ m, the accumulative total volume fraction is that the gradient of 20% o'clock curve is 6.3%/μ m, the accumulative total volume fraction is that the gradient of 80% o'clock curve is 2.5%/μ m, and median size D50 is 9.8 μ m.
With the hydraulic pressure stamping machine at 0.3t/cm 2Pressure under to these powder pressurize processing after, its apparent density is 2.98g/cm 3After particle after the pressurization processing scattered with hand, put into the water ultrasonic dispersing again, the mensuration size distribution, consequently, particle diameter is 0% less than the volume fraction of 1 μ m.
In addition, adopt with the same method of example 1 and obtain the initial stage volume capacity density of anode electrode layer, the heating starting temperature that is charged to 4.3V and is charged to the battery of 4.7V.Used electrolytic solution is the LiPF of concentration 1M 6The initial stage volume capacity density of the anode electrode layer of the battery of/EC+DEC (1: 1) solution is 399mAh/cm 3, the heating starting temperature that is charged to 4.3V and is charged to the battery of 4.7V is respectively 151 ℃ and 87 ℃.In addition, to used concentration of electrolyte be the LiPF of 1M 6The battery of/EC+DEC+EMC (1: 1: 2) solution charges postcooling to-25 ℃ in 25 ℃, standard with the load current of 1g positive active material 75mA discharges into 2.5V then, by obtaining the initial stage loading capacity in-25 ℃, try to achieve 25 ℃ initial capacity is decided to be 100% o'clock capability retention in-25 ℃, capability retention consequently ,-25 ℃ is 89%.
[example 12]
Except being 0.75m with specific surface area 2The tricobalt tetroxide of/g replaces outside the alkali formula cobaltous hydroxide, and other operations are identical with example 1, make LiCoO 2Powder.Adopt the X ray diffracting spectrum that obtains the powder behind the sintering with the same method of example 1, used in the powder x-ray diffraction of CuK α line, near the diffraction peak half-width of (110) face 2 θ=66.5 ± 1 ° is 0.132 °.
Measure through pulverizing and the fractionated median size reaches the accumulative total pore volume of pore diameter 0.006～1 μ m of the powder of about 10 μ m with mercury porosimeter, consequently, pore volume is below 0.01cc/g.
The particle diameter of D5 is 5.76 μ m, the particle diameter of D95 is 15.8 μ m, particle diameter is 0% less than the volume fraction of the particle of 1 μ m, particle diameter is 0% greater than the volume fraction of the particle of 40 μ m, the accumulative total volume fraction is that the gradient of 20% o'clock curve is 10.7%/μ m, the accumulative total volume fraction is that the gradient of 80% o'clock curve is 2.8%/μ m, and median size D50 is 10.2 μ m.
With the hydraulic pressure stamping machine at 0.3t/cm 2Pressure under to these powder pressurize processing after, its apparent density is 2.94g/cm 3After particle after the pressurization processing scattered with hand, put into the water ultrasonic dispersing again, the mensuration size distribution, consequently, particle diameter is 0% less than the volume fraction of 1 μ m.
Adopt with the same method of example 1 and obtain the initial stage volume capacity density of anode electrode layer, the heating starting temperature that is charged to 4.3V and is charged to the battery of 4.7V.The initial stage volume capacity density of the anode electrode layer of battery is 421mAh/cm 3, the heating starting temperature that is charged to 4.3V and is charged to the battery of 4.7V is respectively 151 ℃ and 88 ℃.In addition, to used electrolytic solution be the LiPF of concentration 1M 6The battery of/EC+DEC+EMC (1: 1: 2) solution charges postcooling to-25 ℃ in 25 ℃, standard with the load current of 1g positive active material 75mA discharges into 2.5V then, by obtaining the initial stage loading capacity in-25 ℃, try to achieve 25 ℃ initial capacity is decided to be 100% o'clock capability retention in-25 ℃, capability retention consequently ,-25 ℃ is 86%.
[example 13]
Except with the aqueous chloride solution co-precipitation in alkali that makes nickel and cobalt, to coprecipitate heating and the nickel-cobalt co-precipitation oxyhydroxide (atomic ratio 0.8: 0.2) that obtains substitutes and makes the co-precipitation in carbon dioxide of nickel and cobalt ammine compound, coprecipitate is heated and nickel-cobalt co-precipitation oxyhydroxide (atomic ratio 0.8: 0.2) of obtaining, other operations are identical with example 7, make LiNi 0.80Co 0.20O 2Powder.
Adopt the X ray diffracting spectrum that obtains the powder behind the sintering with the same method of example 7, used in the powder x-ray diffraction of CuK α line, near the diffraction peak half-width of (110) face 2 θ=65 ± 1 ° is 0.115 °.
Measure through pulverizing and the fractionated median size reaches the accumulative total pore volume of pore diameter 0.006～1 μ m of the powder of about 5 μ m with mercury porosimeter, consequently, pore volume is below 0.01cc/g.
The particle diameter of D5 is 3.7 μ m, the particle diameter of D95 is 8.4 μ m, particle diameter is 0% less than the volume fraction of the particle of 1 μ m, particle diameter is 0% greater than the volume fraction of the particle of 40 μ m, the accumulative total volume fraction is that the gradient of 20% o'clock curve is 27.9%/μ m, the accumulative total volume fraction is that the gradient of 80% o'clock curve is 13.5%/μ m, and median size D50 is 5.4 μ m.
With the hydraulic pressure stamping machine at 0.3t/cm 2Pressure under to these powder pressurize processing after, its apparent density is 2.58g/cm 3After particle after the pressurization processing scattered with hand, put into the water ultrasonic dispersing again, the mensuration size distribution, consequently, particle diameter is 0% less than the volume fraction of 1 μ m.
Adopt the initial stage volume capacity density of obtaining the anode electrode layer with the same method of example 7.Used concentration of electrolyte is the LiPF of 1M 6The initial stage volume capacity density of the anode electrode layer of the battery of/EC+DEC (1: 1) solution is 476mAh/cm 3, this initial stage volume capacity density is compared obvious decline with the example 7 with same composition.
[example 14]
Except with the sulfate solution co-precipitation in alkali that makes nickel, cobalt and manganese, to coprecipitate heating and the nickel-cobalt-manganese co-precipitation oxyhydroxide (atomic ratio 0.6: 0.2: 0.2) that obtains substitutes and makes the co-precipitation in carbon dioxide of nickel and cobalt ammine compound, coprecipitate is heated and nickel-cobalt co-precipitation oxyhydroxide (atomic ratio 0.8: 0.2) of obtaining, other operations are identical with example 7, make LiNi 0.60Co 0.20Mn 0.2O 2Powder.
Adopt the X ray diffracting spectrum that obtains the powder behind the sintering with the same method of example 7, used in the powder x-ray diffraction of CuK α line, near the diffraction peak half-width of (110) face 2 θ=65 ± 1 ° is 0.143 °.
Measure through pulverizing and the fractionated median size reaches the accumulative total pore volume of pore diameter 0.006～1 μ m of the powder of about 9 μ m with mercury porosimeter, consequently, pore volume is below 0.01cc/g.
The particle diameter of D5 is 4.75 μ m, the particle diameter of D95 is 13.6 μ m, particle diameter is 0% less than the volume fraction of the particle of 1 μ m, particle diameter is 0% greater than the volume fraction of the particle of 40 μ m, the accumulative total volume fraction is that the gradient of 20% o'clock curve is 6.5%/μ m, the accumulative total volume fraction is that the gradient of 80% o'clock curve is 7.0%/μ m, and median size D50 is 9.1 μ m.
With the hydraulic pressure stamping machine at 0.3t/cm 2Pressure under to these powder pressurize processing after, its apparent density is 3.03g/cm 3After particle after the pressurization processing scattered with hand, put into the water ultrasonic dispersing again, the mensuration size distribution, consequently, particle diameter is 0% less than the volume fraction of 1 μ m.
Adopt the initial stage volume capacity density of obtaining the anode electrode layer with the same method of example 7.Used concentration of electrolyte is the LiPF of 1M 6The initial stage volume capacity density of the anode electrode layer of the battery of/EC+DEC (1: 1) solution is 502mAh/cm 3
[example 15]
Except with the sulfate solution co-precipitation in alkali that makes nickel, cobalt and aluminium, to coprecipitate heating and the nickel-cobalt-aluminium co-precipitation oxyhydroxide (atomic ratio 0.7: 0.2: 0.1) that obtains substitutes and makes the co-precipitation in carbon dioxide of nickel and cobalt ammine compound, coprecipitate is heated and nickel-cobalt co-precipitation oxyhydroxide (atomic ratio 0.8: 0.2) of obtaining, other operations are identical with example 7, make LiNi 0.70Co 0.20Al 0.1O 2Powder.
Adopt the X ray diffracting spectrum that obtains the powder behind the sintering with the same method of example 7, used in the powder x-ray diffraction of CuK α line, near the diffraction peak half-width of (110) face 2 θ=65 ± 1 ° is 0.152 °.
Measure through pulverizing and the fractionated median size reaches the accumulative total pore volume of pore diameter 0.006～1 μ m of the powder of about 8 μ m with mercury porosimeter, consequently pore volume is below 0.01cc/g.The particle diameter of D5 is 3.9 μ m, the particle diameter of D95 is 12.8 μ m, particle diameter is 0% less than the volume fraction of the particle of 1 μ m, particle diameter is 0% greater than the volume fraction of the particle of 40 μ m, the accumulative total volume fraction is that the gradient of 20% o'clock curve is 5.8%/μ m, the accumulative total volume fraction is that the gradient of 80% o'clock curve is 7.5%/μ m, and median size D50 is 8.6 μ m.
With the hydraulic pressure stamping machine at 0.3t/cm 2Pressure under to these powder pressurize processing after, its apparent density is 3.12g/cm 3After particle after the pressurization processing scattered with hand, put into the water ultrasonic dispersing again, the mensuration size distribution, consequently, particle diameter is 0% less than the volume fraction of 1 μ m.
Adopt the initial stage volume capacity density of obtaining the anode electrode layer with the same method of example 7.Used concentration of electrolyte is the LiPF of 1M 6The initial stage volume capacity density of the anode electrode layer of the battery of/EC+DEC (1: 1) solution is 518mAh/cm 3
[example 16]
Except with the sulfate solution co-precipitation in alkali that makes nickel, cobalt and manganese, to coprecipitate heating and the nickel-cobalt-manganese co-precipitation oxyhydroxide (atomic ratio 0.4: 0.3: 0.3) that obtains substitutes and makes the co-precipitation in carbon dioxide of nickel and cobalt ammine compound, coprecipitate is heated and nickel-cobalt co-precipitation oxyhydroxide (atomic ratio 0.8: 0.2) of obtaining, other operations are identical with example 7, make LiNi 0.4Co 0.3Mn 0.3O 2Powder.Can find out from the x-ray diffractogram of powder spectrum of having used CuK α line, be R3-m, have the laminate structure of hexagonal system.
Measure through pulverizing and the fractionated median size reaches the accumulative total pore volume of pore diameter 0.006～1 μ m of the powder of about 10 μ m with mercury porosimeter, consequently, pore volume is below 0.01cc/g.
The particle diameter of D5 is 3.36 μ m, the particle diameter of D95 is 14.8 μ m, particle diameter is 0% less than the volume fraction of the particle of 1 μ m, particle diameter is 0% greater than the volume fraction of the particle of 40 μ m, the accumulative total volume fraction is that the gradient of 20% o'clock curve is 6.5%/μ m, the accumulative total volume fraction is that the gradient of 80% o'clock curve is 6.2%/μ m, and median size D50 is 10.2 μ m.
With the hydraulic pressure stamping machine at 0.3t/cm 2Pressure under to these powder pressurize processing after, its apparent density is 3.09g/cm 3After particle after the pressurization processing scattered with hand, put into the water ultrasonic dispersing again, the mensuration size distribution, consequently, particle diameter is 0% less than the volume fraction of 1 μ m.
Adopt the initial stage volume capacity density of obtaining the anode electrode layer with the same method of example 7.Used electrolytic solution is the LiPF of concentration 1M 6The initial stage volume capacity density of the anode electrode layer of the battery of/EC+DEC (1: 1) solution is 498mAh/cm 3
[example 17]
Except with the sulfate solution co-precipitation in alkali that makes nickel and manganese, to coprecipitate heating and the nickel-manganese co-precipitation oxyhydroxide (atomic ratio 0.5: 0.5) that obtains substitutes and makes the co-precipitation in carbon dioxide of nickel and cobalt ammine compound, coprecipitate is heated and nickel-cobalt co-precipitation oxyhydroxide (atomic ratio 0.8: 0.2) of obtaining, other operations are identical with example 7, make LiNi 0.5Mn 0.5O 2Powder.Can find out from the powder x-ray diffraction that has used CuK α line, be R3-m, have the laminate structure of hexagonal system.
Measure through pulverizing and the fractionated median size reaches the accumulative total pore volume of pore diameter 0.006～1 μ m of the powder of about 9 μ m with mercury porosimeter, consequently, pore volume is below 0.01cc/g.
The particle diameter of D5 is 4.25 μ m, the particle diameter of D95 is 16.5 μ m, particle diameter is 0% less than the volume fraction of the particle of 1 μ m, particle diameter is 0% greater than the volume fraction of the particle of 40 μ m, the accumulative total volume fraction is that the gradient of 20% o'clock curve is 6.5%/μ m, the accumulative total volume fraction is that the gradient of 80% o'clock curve is 5.5%/μ m, and median size D50 is 9.8 μ m.
With the hydraulic pressure stamping machine at 0.3t/cm 2Pressure under to these powder pressurize processing after, its apparent density is 2.96g/cm 3After particle after the pressurization processing scattered with hand, put into the water ultrasonic dispersing again, the mensuration size distribution, consequently, particle diameter is 0% less than the volume fraction of 1 μ m.
Adopt the initial stage volume capacity density of obtaining the anode electrode layer with the same method of example 7.Used electrolytic solution is the LiPF of concentration 1M 6The initial stage volume capacity density of the anode electrode layer of the battery of/EC+DEC (1: 1) solution is 450mAh/cm 3
The possibility of utilizing on the industry
By the present invention can obtain having bigger volume capacity density, the lithium-transition metal composite oxide of the novelty that is suitable as positive active material for lithium secondary battery of higher security, good even screening characteristics, favorable charge-discharge cyclic durability, good cold property.
Table 1
Particle diameter μ m Accumulative total % Frequency % Particle diameter μ m Accumulative total % Frequency %
?0.97 ?0.00 ?0.00 ?6.54 ?19.23 ?3.42
?1.06 ?0.00 ?0.00 ?7.13 ?23.20 ?3.97
?1.16 ?0.00 ?0.00 ?7.78 ?27.92 ?4.72
?1.26 ?0.00 ?0.00 ?8.48 ?33.56 ?5.64
?1.38 ?0.00 ?0.00 ?9.25 ?40.21 ?6.65
?1.50 ?0.00 ?0.00 ?10.09 ?47.93 ?7.72
?1.64 ?0.00 ?0.00 ?11.00 ?56.40 ?8.47
?1.78 ?0.00 ?0.00 ?12.00 ?65.27 ?8.87
?1.95 ?0.00 ?0.00 ?13.08 ?73.86 ?8.59
?2.12 ?0.00 ?0.00 ?14.27 ?81.50 ?7.64
?2.31 ?0.00 ?0.00 ?15.56 ?87.82 ?6.32
?2.52 ?0.10 ?0.10 ?16.96 ?92.50 ?4.68
?2.75 ?0.32 ?0.22 ?18.50 ?95.77 ?3.27
?3.00 ?0.73 ?0.41 ?20.17 ?97.80 ?2.03
?3.27 ?1.40 ?0.67 ?22.00 ?99.00 ?1.20
?3.57 ?2.44 ?1.04 ?23.99 ?100.00 ?0.68
?3.89 ?3.84 ?1.40 ?26.16 ?100.00 ?0.32
?4.24 ?5.62 ?1.78 ?28.53 ?100.00 ?0.00
?4.63 ?7.74 ?2.12 ?31.11 ?100.00 ?0.00
?5.04 ?10.13 ?2.39 ?33.93 ?100.00 ?0.00
?5.50 ?12.82 ?2.69 ?37.00 ?100.00 ?0.00
?6.00 ?15.81 ?2.99 ?40.35 ?100.00 ?0.00
Table 2
Particle diameter μ m Accumulative total % Frequency % Particle diameter μ m Accumulative total % Frequency %
?0.97 ?0.00 ?0.00 ?6.54 ?17.52 ?6.06
?1.06 ?0.00 ?0.00 ?7.13 ?25.28 ?7.76
?1.16 ?0.00 ?0.00 ?7.78 ?34.42 ?9.14
?1.26 ?0.00 ?0.00 ?8.48 ?44.55 ?10.13
?1.38 ?0.00 ?0.00 ?9.25 ?54.97 ?9.97
?1.50 ?0.00 ?0.00 ?10.09 ?64.94 ?9.00
?1.64 ?0.00 ?0.00 ?11.00 ?73.94 ?7.52
?1.78 ?0.00 ?0.00 ?12.00 ?81.46 ?5.98
?1.95 ?0.00 ?0.00 ?13.08 ?87.44 ?4.42
?2.12 ?0.00 ?0.00 ?14.27 ?91.86 ?3.13
?2.31 ?0.00 ?0.00 ?15.56 ?94.99 ?2.07
?2.52 ?0.00 ?0.00 ?16.96 ?97.06 ?1.31
?2.75 ?0.00 ?0.00 ?18.50 ?98.37 ?0.79
?3.00 ?0.00 ?0.00 ?20.17 ?99.16 ?0.45
?3.27 ?0.00 ?0.00 ?22.00 ?99.61 ?0.26
?3.57 ?0.11 ?0.11 ?23.99 ?99.87 ?0.13
?3.89 ?0.38 ?0.27 ?26.16 ?100.00 ?0.00
?4.24 ?0.96 ?0.58 ?28.53 ?100.00 ?0.00
?4.63 ?2.05 ?1.09 ?31.11 ?100.00 ?0.00
?5.04 ?3.96 ?1.91 ?33.93 ?100.00 ?0.00
?5.50 ?6.98 ?3.02 ?37.00 ?100.00 ?0.00
?6.00 ?11.46 ?4.48 ?40.35 ?100.00 ?0.00

Claims (15)

1. lithium-transition metal composite oxide is characterized in that, contains general formula Li xM 1-yN yO 2The lithium composite xoide particle of expression, in the formula, 0.2≤x≤1.2,0≤y≤0.7, M are transition metal, N is M transition metal or alkali earth metal in addition, in the accumulative total volume particle size distribution curve of this lithium composite xoide, the accumulative total volume fraction is that the gradient of 20% o'clock curve is below 9%/μ m, the accumulative total volume fraction be the gradient of 80% o'clock curve more than 3%/μ m, and median size is 3～20 μ m.
2. lithium-transition metal composite oxide as claimed in claim 1, wherein, below 0.1%, and particle diameter surpasses the accumulative total volume fraction of particle of 40 μ m below 0.5% to particle diameter less than the accumulative total volume fraction of the particle of 1 μ m.
3. lithium-transition metal composite oxide as claimed in claim 1 or 2, wherein, volume reference accumulative total 5% footpath is more than 2 μ m, and volume reference accumulative total 95% footpath is below 30 μ m.
4. as each described lithium-transition metal composite oxide in the claim 1～3, wherein, the accumulative total volume fraction is that the gradient of 20% o'clock curve is below 7.5%/μ m, the accumulative total volume fraction is that the gradient of 80% o'clock curve is more than 4.5%/μ m, and particle diameter less than the volume fraction of the particle of 1 μ m below 0.01%, particle diameter surpasses the volume fraction of particle of 40 μ m below 0.1%, and volume reference accumulative total 5% footpath is more than 3 μ m, and volume reference accumulative total 95% footpath is below 20 μ m.
5. as each described lithium-transition metal composite oxide in the claim 1～4, wherein, at 0.3t/cm 2Pressure under the lithium-transition metal composite oxide powder is pressurizeed after the compression, particle diameter less than the volume fraction of the particle of 1 μ m below 0.1%.
6. as each described lithium-transition metal composite oxide in the claim 1～5, wherein, M is Co.
7. as each described lithium-transition metal composite oxide in the claim 1～6, wherein, M is Co, be that the diffraction peak half-width of (110) face of 2 θ=66.5 ± 1 measured of radiogenic X-ray diffraction ° is 0.070～0.110 ° with CuK α, and y is 0.
8. as each described lithium-transition metal composite oxide in the claim 1～6, wherein, M is Co, with CuK α is that the diffraction peak half-width of (110) face of 2 θ=66.5 ± 1 measured of radiogenic X-ray diffraction ° is 0.080～0.180 °, and N is selected from Ti, Zr, Hf, V, Nb, Ta at least a kind, and y satisfies 0.0005≤y≤0.02.
9. as each described lithium-transition metal composite oxide in the claim 1～5, wherein, M is Ni.
10. as each described lithium-transition metal composite oxide in the claim 1～5, wherein, M is Ni, and N is Co, 0.1≤y≤0.4, and be that the diffraction peak half-width of (110) face of 2 θ=65 ± 1 measured of radiogenic X-ray diffraction ° is 0.13～0.20 ° with CuK α.
11. as each described lithium-transition metal composite oxide in claim 1～5 or 9, wherein, M is Ni, N is Mn, 0.4≤y≤0.6.
12. as each described lithium-transition metal composite oxide in claim 1～5 or 9, wherein, M is Ni, N is Co and Mn, 0.4≤y≤0.7, and the atomic ratio of Co/Mn is 1/4～4/1.
13. as each described lithium-transition metal composite oxide in claim 1～5 or 9, wherein, M is that Ni, N are Co and Al or Mn, 0.1≤y≤0.4, and the atomic ratio of Co/ (Al or Mn) is 1/4～4/1.
14. the secondary lithium batteries positive pole is characterized in that, is positive active material with each described lithium-transition metal composite oxide in the claim 1～13.
15. lithium secondary battery is characterized in that, has the described positive pole of claim 14.
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